Cellulose article and method of making the same



Patented 2 0, 1925}.

E STATE re atta FFHQQ JOHN FEITH, OF DENVER, COLORADO, AND JOHN W. ZIEGLER, OF KOKOMO, INDIANA,

ASSIGNORS TO JAMES CLARENCE PATTEN, OF KOKO'MO, INDIANA.

I GELLULOSE ARTICLE AND METHOD or MAKING THE SAME.

' No Drawing. Original application filed December 8, 1921, Serial No. 521,031, Divided and this ap- V plication filed. April 6, 1923. Serial No. 630,412..

To all who-met may concern:- Be it known that we, 1) JOHN FEITH and (2) JOHN WESLEY ZIEGLER, both citizens of the United States, residing'at (1) Denver, 5 (2) Kokomo, in the-counties of 1) Denver, (2) Howard, and States of (1) .Colorad0, (2) Indiana, have invented certain new and useful Improvements in Cellulose Articles and Methods of Making the Same, of which the following is a specification. This invention relates to a new and improved'me-thod for making cellulose articles and-in particular to methods involving the 2 use of copper ammonium cellulose solutions. After considerable experimentation and research in this particular branch of the cellulose field, we have found a much quicker,-more' efficient, and cheaper method of making up acupro-ammonium cellulose solution of such concentration and composition that will, in certain after steps, produce a cellulose, which has very desirable physical and chemical properties. This cellulose so produced, particularly in sheet form, has properties which are markedly different from the cellulose produced from similar solutions, as: for instance, artificial silk, which has been formed by coagulation in a chemical medium and afterwards dried! In the process for the employment of this solution that we have developed, it is not our practice to follow the usual methods ofobtaining cellulose from such c,upr0-ammonium solutions, namely, by chemicalcoagulation: but'to allow our solutions to set in the air upon suitable plates, tables or belts. By the methods heretofore; used a long time is required for the proper preparation of the cupric hydroxide used. The solutions prepared by our method need not be seasoned or aged before they can be used, and the expense incident to carrying a; stock of solution is thereby obviated. In our method we can 'makeup commercial batches and have the same ready for commercial use inside of five to six hours. Furthermore, our

solutions are economical in the relation of the cupric hydroxide to the cotton dissolved.

The following is a full and complete description of our method of preparing a cupric-ammonium cellulose solution and obtaining from the same cellolose in a useful form and of unique properties. We have found that by taking dry cupric hydroxide, commercial aqueous ammonia (sp. gr. about 0.9) and cotton linters, filter paper scrap or cotton rags, and masticating them together at ordinary temperatures, we can obtain a richer cellulose solution in a shorter time than by any of the present known methods.

A representative formula is as follows: 910 grams ammonium hydroxide (0.9 sp'. g1'.), 40 grams cupric hydroxide, grams cotton.

The ammonium hydroxide is placed in a suitable container, which may, for instance, be of glass, and to this is added the cuprichydroxide while stirring. The cotton is then added while stirring. The stirring is continued for 10 minutes after the final cotton has been added and in this time the cotton is completely gelatinized, and the solution fairly viscous. The solution as prepared from the above formula is a 5% cotton solution, but we do not wish to limit ourselves to this single composition. We have found that we can readily make solutions richer in cotton and that contain up to 9% cellulose in solution. We can, of course, make solutions from any low percentage up to this point, and in doing so need only vary the relation between the am monium hydroxide solution, copper hydroxide and the cotton.

Though solutions made up of thethree constituents above noted will result in the production of a cellulose material having the described physical properties, yet we prefer to use an addition agent, such as glycerin, starch, glucose or the like at the time of making up the solution, as we find that the employment of same has certain of the addition agent employed and its relation to the other constituents, namely: 900

grams ammonium hydroxide (0.9 sp."gr.),

lOgrams cupric hydroxide, 550 grams cotton, '10 grams glycerine.

All these solutions are made up as much aspossible out of contact with the air to' prevent the formation of oxycellulose. They are next filtered to free them from dirt and foreign matter, using a centrifuge or pressure filter for this operation. The clarified solution is then vacuum-treated for a :hort period of time, the solution being maintained at a temperature of about 90 F., and and by this processing the excess of ammonia is removed and afterwards recovered, there remaining in the solution approximately three to five percent by weight of ammonia gas. This solution, which may bea batch of 500 pounds, may be made up ready for pouring in five tosix hours. The next step is the pouring of this material from a suitable container, provided with a slit or the like, onto the surface of a glass or metal plate or table. It is allowed to cover the surface of this level table to a predetermined depth, depending upon the thickness required and there it will set to a compact film in a time period varying between one to three hours. This time of setting depends'upon the con- 'centration of the solution and the thickness be used.

The pouring and drying table is prefer-Q ably provided with means for heating from.

below and the temperatureof the surface: of

the plate is maintained slightly above'the' room temperature. This is to offset the cool-; ing eifect of evaporation and to enable the film to dry-from the bottom up, and to pre' vent "decomposition at the, bottom of mass caused by excessive cooling. Y As an exam le, of the amount-required to i get a given thickness offinished cellulose, if

2 cc. of 5% cotton solution are allowed to coverone squareflinch of plate surface,the final finished cellulose will be approximately .005 thick. 7

After the cup'rosammoniu-m cellulose solution has set upon the table, it has changed from a viscous solution to a solid sheet, which is evenly translucent, of a deep blue color, and evenly thick throughout its entire area. It has a peculiar iridescent, pearly finish, and is quite tough and rubber-like to the touch. When this stage is reached, the

sheet is covered with-water which is allowed 'tained in the sheet.

reabsorption of water. time it will absorb some water but will redried under tension. p This cellulose has many uses. It canbe to remain for about fifteen minutes. This water extracts some of the ammonia still re- This ,water is then drawn oil and is replaced with a weak acid solution, preferably about a 5% sulphuric acid solution. This acid solution breaks up the copper ammonia cellulose, removing the copper and ammonium as sulphates which pass into a water solution and leave the sheet ofa-light whitish green color, translucent and very strong. During this step the area of the sheet shrinks considerably, in some cases amounting to approximately 20%. When this operation is finished the sheet, which was previously firmly attached to the table top, is now loose so that it can be lifted from the table. It is now placed in another weak acid bath for a period of about one and ammonia salts. It is then rinsed oil with distilled water and placed in a tank supplied with running water to complete the removal'of the copper and ammonium salts and free acid from the stock of thesheet.

The next operation is one .in which the cellulose acquires its final form, condition and shape, and is carried out on suitable racks which hold the edges of the sheet and permit it to dry under tension. The shrinkage in this step isconsiderable, but occurs only in one plane, viz :-in its thickness. In this drying the thickness will change from approximately .040 to .005". The appearance of the sheet has now changed from a whitish translucent material to a waterwhite absolutely transparent article. The dried product is no longer soft and rubbery, but is hard enough-to resist the finger nail and is fairly resilient and flexible. It will not regain its original thickness or area by If wetted. for some gain its original dried dimension when again internally sensitized by soaking it in alkali metal bromide or iodide solutions and then in sllver nitrate solution, forming within itself light sensitive silver. compounds, so that it mayi be used as aphotographic film. Other solid-pigments may be formed in its mass by substituting other impregnating baths. .Such treated cellulose after drying and treatment with, for instance, glycerine can be used as an artificial leather. In fact,

in many places where celluloid is now used this cellulose stock can be substituted. It

is not explosively combustible like celluloid but burns like a woven cotton fabric. It is not hygroscopic. i

The above described cellulose-copper-ammonium-solution can also be used in the roduction of artificial silks and other colloidal products, description of which is given in our other patent application.

1. The method ofmaking cupro-amm0nium cellulose Solutions which consists in adding cupric hydroxideto ammonium hydroxide while stirring; adding cellulosic material while the agitation is. continued, filtering the resultant solution and removing the excess of ammonia by heating in a vacuum. 2. The method as claimed in claim 1 in I which an addition agent is added at the time the solution 'is made.

In testimony whereof, we affix our signatures.

- JOHN FEITH.

. JOHN W. ZIEGLER. 

